US11041236B2 - Method for direct patterned growth of atomic layer metal dichalcogenides with pre-defined width - Google Patents

Method for direct patterned growth of atomic layer metal dichalcogenides with pre-defined width Download PDF

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US11041236B2
US11041236B2 US16/290,407 US201916290407A US11041236B2 US 11041236 B2 US11041236 B2 US 11041236B2 US 201916290407 A US201916290407 A US 201916290407A US 11041236 B2 US11041236 B2 US 11041236B2
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patterns
substrate
salt
carbon nanostructures
metal
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US20200277699A1 (en
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Avetik Harutyunyan
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Honda Motor Co Ltd
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Priority to CN202010092018.4A priority patent/CN111640648B/zh
Priority to JP2020023462A priority patent/JP7018980B2/ja
Priority to DE102020104284.1A priority patent/DE102020104284B4/de
Priority to KR1020200020753A priority patent/KR102360405B1/ko
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    • H05K3/00—Apparatus or processes for manufacturing printed circuits
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/042—Coating on selected surface areas, e.g. using masks using masks
    • C—CHEMISTRY; METALLURGY
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
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    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/305—Sulfides, selenides, or tellurides
    • C—CHEMISTRY; METALLURGY
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
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    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
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    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present disclosure is directed generally to a method of growing patterns of an atomic layer of metal dichalcogenides.
  • the present disclosure is directed to a method of growing patterns of an atomic layer of metal dichalcogenides, particularly transition metal dichalcogenides, having a pre-defined width, and in particular, a sub-five nanometer width.
  • the method may comprise the steps of providing a substrate; providing aligned patterns of carbon nanostructures on the substrate; providing a metal in contact with at least two separate portions of the patterns of carbon nanostructures; depositing a salt layer on the substrate and the patterns of carbon nanostructures; resistively heating the patterns of carbon nanostructures to remove the patterns of carbon nanostructures and the salt deposited thereon, wherein removing the patterns of carbon nanostructures and the salt deposited thereon provides salt patterns corresponding to the remaining salt layer; and growing an atomic layer of metal dichalcogenides on the salt patterns, wherein the atomic layer of metal dichalcogenides is provided in aligned patterns having a pre-defined width.
  • the present disclosure is also directed to the patterns of metal dichalcogenides provided by the method as described herein and methods of using
  • FIG. 1 shows an example substrate having aligned strips of carbon nanostructures deposited thereon, according to aspects of the present disclosure.
  • FIG. 2 shows an example of a metal provided in contact with at least two separate portions of patterns of carbon nanostructures, according to aspects of the present disclosure.
  • FIG. 3 shows an example of a salt layer deposited on a substrate and patterns of carbon nanostructures, according to aspects of the present disclosure.
  • FIG. 4 shows an electrical network, according to aspects of the present disclosure.
  • FIG. 5 shows a substrate having patterns of substrate material and patterns of an atomic layer of metal dichalcogenides, according to aspects of the present disclosure.
  • FIG. 6A shows an example method of growing aligned patterns of carbon nanostructures, according to aspects of the present disclosure.
  • FIG. 6B shows an example method of growing aligned patterns of carbon nanostructures, according to aspects of the present disclosure.
  • the present disclosure is directed to a method of growing patterns of an atomic layer of metal dichalcogenides, particularly transition metal dichalcogenides, having a pre-defined width, and in particular, a sub-five nanometer width.
  • the method may comprise the steps of providing a substrate; providing aligned patterns of carbon nanostructures on the substrate; providing a metal in contact with at least two separate portions of the patterns of carbon nanostructures; depositing a salt layer on the substrate and the patterns of carbon nanostructures; resistively heating the patterns of carbon nanostructures to remove the patterns of carbon nanostructures and the salt deposited thereon, wherein removing the patterns of carbon nanostructures and the salt deposited thereon provides salt patterns corresponding to the remaining salt layer; and growing an atomic layer of metal dichalcogenides on the salt patterns, wherein the atomic layer of metal dichalcogenides is provided in aligned patterns having a pre-defined width.
  • the present disclosure is also directed to the patterns of metal dichalcogenides provided by the method as described herein and methods of using
  • the method may comprise providing a substrate.
  • the substrate may be any inert material suitable for use according to the methods as described herein.
  • substrates useful according to the present disclosure include, but are not limited to, substrates comprising or consisting of SiO 2 , Si, c-sapphire, fluorophlogopite mica, SrTiO 3 , h-BN, or combinations thereof. It should be understood that where a SiO 2 substrate is described herein as an example substrate, any suitable substrate may be used in addition to or instead of the same.
  • the method may comprise providing aligned patterns of carbon nanostructures on the substrate.
  • the term “pattern” refers to a configured shape of a material.
  • the aligned patterns of carbon nanostructures may comprise aligned “strips” of carbon nanostructures, alternatively referred to herein as “bands” or “ribbons.”
  • the term “aligned” refers to an alignment wherein two or more patterns are oriented to provide an approximately constant distance therebetween.
  • FIG. 1 shows a substrate 11 , such as an SiO 2 substrate, having aligned strips of carbon nanostructures 12 deposited thereon.
  • the aligned strips of carbon nanostructures 12 may be provided so as to extend from about a first end 16 of the substrate 11 to about a second end 17 of the substrate 11 .
  • a first strip 121 of the aligned strips of carbon nanostructures 12 is aligned with a second strip 122 of the aligned strips, such that a distance 15 between the first strip 121 and the second strip 122 is approximately constant along the length 13 of the substrate.
  • the patterns may be horizontally aligned. It should be understood that the term “horizontal” in the context of the present disclosure, and in particular, in the context of FIG.
  • the terms “horizontal,” “vertical,” “length,” and “width” should not necessarily limit the orientation of the patterns of carbon nanostructures and/or the substrate in space. It should also be understood that while the figures herein show an example substrate having a rectangular shape with a length 13 that is greater than the width 14 , the substrate may have any shape acceptable for use with the methods as described herein, including, but not limited to, a polygonal shape (triangular, square, pentagonal, hexagonal, etc.), an elliptic shape (circular, oval-shaped, etc.), and combinations thereof.
  • nanostructure refers to a structure having at least one dimension on the nanoscale, that is, at least on dimension between about 0.1 and 100 nm. It should be understood that “nanostructures” include, but are not limited to, nanosheets, nanotubes, nanoparticles (e.g., polyhedral nanoparticles), nanopsheres, nanowires, nanocubes, and combinations thereof.
  • a nanosheet may comprise a sheet having a thickness on the nanoscale.
  • a nanotube may comprise a tube having a diameter on the nanoscale.
  • a nanoparticle may comprise a particle wherein each spatial dimension thereof is on the nanoscale.
  • the carbon nanostructures may comprise copper nanotubes, including, but not limited to, single-walled nanotubes (SWNTs), multi-walled nanotubes (MWNTs), and combinations thereof.
  • SWNTs and/or MWNTs may have a dimeter that is between about 0.1 and 100 nm, optionally between about 0.1 and 50 nm, optionally between about 0.1 and 25 nm, optionally between about 0.1 and 10 nm, optionally between about 0.1 and 5 nm, and optionally about 1 nm.
  • aligned patterns of carbon nanostructures may be provided on the substrate by any means known in the art compatible with the present disclosure, including, but not limited to, chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • the aligned patterns of carbon nanostructures may be provided on the substrate by providing a colloidal dispersion of catalyst particles on the substrate and growing carbon nanostructures thereon by CVD and/or by providing a colloidal dispersion of catalyst precursor particles on the substrate, heating the catalyst precursor particles to form catalyst particles, and growing carbon nanostructures thereon by CVD.
  • FIG. 6A shows an example method of growing aligned patterns of carbon nanostructures as described herein.
  • FIG. 6A shows a substrate 61 having catalyst particles 62 provided near a first end 63 thereof.
  • a carbon source gas may be provided, optionally with a carrier gas such as an inert gas.
  • the carbon source and/or inert gas may be provided at a sufficient flow rate such that growth of carbon nanostructures 64 proceeds in a selected direction, for example, toward a second end 65 of the substrate 61 .
  • sufficient flow rates include, but are not limited to, at least 1000 sccm, optionally at least 2000 sccm, and optionally at least 3000 sccm.
  • aligned patterns of carbon nanostructures 64 may be provided, the patterns extending from a first end 63 of the substrate 61 to a second end 65 of the substrate 61 . It should be understood that upon each catalyst particle 62 , one nanostructure may grow. Alternatively, upon each catalyst particle 62 , two or more nanostructures may grow.
  • FIG. 6B shows another example method of growing aligned patterns of carbon nanostructures as described herein. Similar to the example shown in FIG. 6A , the example shown in FIG. 6B may comprise providing a catalyst 66 near a first end 63 of a substrate 61 . As shown in FIG. 6B , the catalyst 66 may comprise a thin film strip of catalyst material, e.g., a film having a thickness of between about 5 and 20 nm. The thin film strip of catalyst material 66 may then be subjected to a thermal treatment in an inert environment in order to provide discrete catalyst particles 62 , similar to the catalyst particles 62 shown in FIG. 6A . The method may then proceed as described in relation to FIG. 6A , that is, a carbon source gas and optionally a carrier gas may be provided at a sufficient flow rate such that growth of carbon nanostructures 64 proceeds in a selected direction, for example, toward a second end 65 of the substrate.
  • a carbon source gas and optionally a carrier gas may be provided at
  • a mask may be used to provide the thin film strip of catalyst material on the substrate as described herein.
  • the mask may be removed and the thin film strip of catalyst material may be subjected to a thermal treatment as described herein to provide catalyst particles.
  • a lithography process may be used to provide the thin film strip of catalyst material and/or the catalyst particles on the substrate.
  • Examples of carbon sources useful according to the present disclosure include, but are not limited to, a hydrocarbon, an alcohol, an ester, a ketone, an aromatic, an aldehyde, and a combination thereof.
  • the carbon source may be selected from xylene, propane, butane, butene, ethylene, ethanol, carbon monoxide, butadiene, pentane, pentene, methane, ethane, acetylene, carbon dioxide, naphthalene, hexane, cyclohexane, benzene, methanol, propanol, propylene, commercial fuel gases (such as liquefied petroleum gas, natural gas, and the like), and combinations thereof.
  • inert gases include, but are not limited to, gases comprising helium (He), radon (Rd), neon (Ne), argon (Ar), xenon (Xe), nitrogen (N), and combinations thereof.
  • the catalyst material as described herein may be any catalyst known in the art compatible with use according to the present disclosure, including materials containing Fe, Ni, Co, Mo, Cu, Pt, Pd, Ru, Au, Ag, W and alloys thereof.
  • the method may comprise providing a metal in contact with at least two separate portions of the patterns of carbon nanostructures.
  • the metal may be provided using a mask (e.g., a mask that exposes only the at least two separate portions of the patterns of carbon nanostructures) and/or a lithography process.
  • the metal according to the present disclosure may comprise a metal capable of forming an electrical network with at least a voltage source and the carbon nanostructures, as described herein. Examples of metals useful according to the present disclosure include, but are not limited to, nickel (Ni), titanium (Ti), copper (Cu), gold (Au), and combinations thereof.
  • FIG. 2 shows an example of a metal provided in contact with at least two separate portions of the patterns of carbon nanostructures.
  • FIG. 2 shows a substrate 11 having aligned strips of carbon nanostructures 12 deposited thereon, as described in relation to FIG. 1 .
  • FIG. 2 further shows a first metal portion 21 and a second metal portion 22 separate from each other. As shown in FIG. 2 , both the first metal portion 21 and the second metal portion 22 are in contact with the aligned strips of carbon nanostructures 12 , for example, at or near the first end 16 and the second end 17 of the substrate 11 , respectively.
  • the first metal portion 21 and the second metal portion 22 may comprise the same or different metals, so long as they both comprise at least one metal as described herein.
  • first metal portion 21 and the second metal portion 22 may further be provided with wiring 23 that is capable of forming an electrical network with a voltage source, the metal portions, and the carbon nanostructures, as described herein.
  • the wiring may comprise a metal as described herein, which may be the same as or different from the metal(s) comprised by the first metal portion 21 and/or the second metal portion 22 .
  • the method may comprise depositing a salt on the substrate and the patterns of carbon nanostructures.
  • salt refers to an electrically neutral ionic compound having cation(s) and anion(s).
  • Examples of salts usefulness according to the present disclosure include, but are not limited to, sodium salts and potassium salts, such as NaBr, NaCl, KBr, KCl, and combinations thereof. It should be understood that while NaBr is used herein as an example salt, any suitable salt may be used in addition to or instead of the same.
  • FIG. 3 shows an example of a salt layer deposited on the substrate and the patterns of carbon nanostructures.
  • FIG. 3 shows a substrate 11 having aligned strips of carbon nanostructures 12 deposited thereon, as described in relation to FIG. 1 and FIG. 2 .
  • FIG. 3 further shows a salt layer 31 covering a portion of the substrate and the patterns of carbon nanostructures 12 .
  • the salt layer may cover at least about 50% of the surface area of the substrate 11 and/or the patterns of carbon nanostructures 12 , optionally at least about 60%, optionally at least about 70%, optionally at least about 80%, optionally at least about 90%, and optionally at least about 100%.
  • the salt layer be provided on the substrate and/or the patterns of carbon nanostructures by any means known in the art compatible with the present disclosure, including, but not limited to, thermal deposition.
  • the method may comprise resistively heating the patterns of carbon nanostructures to remove the patterns of carbon nanostructures and the portion of the salt layer deposited thereon.
  • resistive heating refers to a process wherein the passage of an electric current through a conductor produces heat.
  • resistive heating may be performed by forming an electrical network comprised by one or more of the components as described herein.
  • FIG. 4 shows an electrical network formed by a voltage source 41 , metal portions 21 and 22 , wiring 23 , and carbon nanostructures (not shown in FIG. 4 ), as described herein.
  • etching refers to the process of corroding a material.
  • etching carbon nanostructures may comprise oxidation of the carbon nanostructures via resistive heating in the presence of oxygen resulting in corrosion of the carbon nanostructures.
  • etching carbon nanostructures may comprise decomposition and/or evaporation of the carbon nanostructures in a vacuum or inert atmosphere.
  • the method may comprise resistively heating the patterns of carbon nanostructures such that complete etching of the carbon nanostructures is achieved, that is, at least about 90% of the patterns of carbon nanostructures is removed, optionally at least about 95%, and optionally at least about 100%.
  • the substrate 11 may also comprise patterns of salt 43 thereon.
  • the patterns of salt 43 correspond to the remaining salt layer 31 , as described in relation to FIG. 3 , that is, the portion of the salt layer 31 that was not removed during resistive heating.
  • the patterns of salt may thus correspond to the patterns of carbon nanostructures 12 removed during resistive heating, and in particular, may correspond to the area of the substrate 11 that was not covered by the patterns of carbon nanostructures 12 in earlier steps of the method.
  • the patterns of salt 43 will comprise strips having a width corresponding to the distance between the patterns of carbon nanostructures 12 .
  • FIG. 4 shows a strip of salt 45 having a width 44 . This width may correspond to the distance 15 between the first strip 121 and the second strip 122 shown in FIG. 1 .
  • the patterns of salt 43 may therefore comprise aligned “strips,” as described herein, wherein each strip has a pre-determined width.
  • the width of each salt strip may be no more than about 50 nm, optionally no more than about 25 nm, optionally no more than about 10 nm, optionally no more than about 7 nm, optionally no more than about 5 nm, and optionally no more than about 1 nm.
  • the method may further comprise growing an atomic layer of metal dichalcogenides on the patterns of salt.
  • metal dichalcogenides useful according to the present disclosure include, but are not limited to, molybdenum disulfide (MoS 2 ), molybdenum diselenide (MoSe 2 ), tungsten disulfide (WS 2 ), and combinations thereof.
  • the atomic layer of metal dichalcogenides may be grown on the patterns of salt by any means known in the art compatible with the present disclosure.
  • the atomic layer of metal dichalcogenides may be grown on the patterns of salt by thermally co-depositing a metal oxide and a chalcogen onto the patterns of salt.
  • molybdenum dioxide MoO 2
  • S sulfur
  • the metal dichalcogenide may comprise WS 2 and/or MoSe 2 by using tungsten dioxide (WO 2 ) and/or tungsten trioxide (WO 3 ) as a metal oxide as described herein and/or by using selenium (Se) as a chalcogen as described herein.
  • the atomic layer of metal dichalcogenides may be grown on the patterns of salt according to the methods described in U.S. patent application Ser. No. 16/217,845, filed Dec. 12, 2018, the disclosure of which being incorporated herein in its entirety by reference. It should be understood that U.S. patent application Ser. No. 16/217,845 further discloses example materials that may be used to provide at least a portion of the atomic layer of metal dichalcogenides as described herein.
  • FIG. 5 shows the substrate 11 as shown in FIG. 4 , that is, the substrate 11 having patterns of the substrate material 42 revealed during resistive heating.
  • FIG. 5 also shows patterns of an atomic layer of metal dichalcogenides 51 grown on the patterns of salt (not shown).
  • the patterns of the atomic layer of metal dichalcogenides 51 may correspond with the patterns of salt 43 as shown in FIG. 4 , and in particular, may comprise aligned “strips,” as described herein, wherein each strip has a pre-determined width.
  • the width of each strip may be no more than about 50 nm, optionally no more than about 25 nm, optionally no more than about 10 nm, optionally no more than about 7 nm, optionally no more than about 5 nm, and optionally no more than about 1 nm.
  • the present disclosure is also directed to patterns of an atomic layer of metal dichalcogenides having a pre-defined width, as described herein.
  • the patterns of an atomic layer of metal dichalcogenides may comprise ribbons of MoS 2 , MoSe 2 , WS 2 , or a combination thereof, wherein each ribbons has a width of no more than about 50 nm, optionally no more than about 25 nm, optionally no more than about 10 nm, optionally no more than about 7 nm, optionally no more than about 5 nm, and optionally no more than about 1 nm.
  • the present disclosure is also directed to circuits comprising the patterns of the atomic layer of metal dichalcogenides as described herein.
  • the term “about” is defined to being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the term “about” is defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.
  • example is used herein to mean “serving as an example, instance, or illustration.” Any aspect described herein as “example” is not necessarily to be construed as preferred or advantageous over other aspects. Unless specifically stated otherwise, the term “some” refers to one or more.
  • Combinations such as “at least one of A, B, or C,” “at least one of A, B, and C,” and “A, B, C, or any combination thereof” include any combination of A, B, and/or C, and may include multiples of A, multiples of B, or multiples of C.
  • combinations such as “at least one of A, B, or C,” “at least one of A, B, and C,” and “A, B, C, or any combination thereof” may be A only, B only, C only, A and B, A and C, B and C, or A and B and C, where any such combinations may contain one or more member or members of A, B, or C.

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JP2020023462A JP7018980B2 (ja) 2019-03-01 2020-02-14 所定の幅を有する原子層金属ジカルコゲナイドの直接パターン化成長方法
DE102020104284.1A DE102020104284B4 (de) 2019-03-01 2020-02-18 Verfahren zum direkten strukturierten erzeugen einer atomaren schicht von metalldichalcogeniden mit vordefinierter breite
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